Herbicidal sulfonamides

ABSTRACT

This invention pertains to benzenesulfonamides and their use as agricultural chemicals.

RELATED APPLICATIONS

This application is a divisional application of my copending applicationU.S. Ser. No. 152,021 filed May 30, 1980, U.S. Pat. No. 4,452,628, whichis a continuation in part of my application U.S. Ser. No. 060,869, filedJuly 26, 1979, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to benzenesulfonamides which are useful asagricultural chemicals.

French Pat. No. 1,468,747 discloses the following para-substitutedphenylsulfonamides, useful as antidiabetic agents: ##STR1## where R=H,halogen, CF₃ or alkyl.

Logemann et al., Chem. Abstr., 53, 18052 g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR2## wherein R is butyl, phenyl or ##STR3## and R₁ is hydrogen ormethyl. When tested for hypoglycemic effect in rats (oral doses of 25mg/100 L g), the compounds in which R is butyl or phenyl were mostpotent. The others were of low potency or inactive.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Abstr.,59, 1633e] describes the synthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl-4-methylbenzenesulfonamide:##STR4## Based upon similarity to a known compound, the author predictedhypoglycemic activity for the foregoing compound.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches thepreparation of compounds of Formula (i), and their use as general orselective herbicides: ##STR5## wherein R₁ and R₂ may independently bealkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

Compounds of Formula (ii), and their use as antidiabetic agents, arereported in J. Drug. Res. 6, 123 (1974): ##STR6## wherein R is pyridyl.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodneeds, such as soybeans, wheat and the like. The current populationexplosion and concomitant world food shortage demand improvements in theefficiency of producing these crops. Prevention or minimizing the lossof a portion of such valuable crops by killing, or inhibiting the growthof undesired vegetation is one way of improving this efficiency.

A wide variety of materials useful for killing or inhibiting(controlling) the growth of undesired vegetation is available; suchmaterials are commonly referred to as herbicides. The need exists,however, for still more effective herbicides that destroy or retardweeds without causing significant damage to useful crops.

SUMMARY OF THE INVENTION

According to this invention, there is provided compounds of Formula (I)and their agriculturally suitable salts, suitable agriculturalcompositions containing them, and methods of using them as selective, aswell as general herbicides having both pre-emergence and post-emergenceactivity. These compounds are highly active herbicides. They areespecially useful for controlling weeds in wheat. ##STR7## wherein W isO or S;

R is CHF₂, CF₃, CH₂ CF₃ or CF₂ CHFG, where G is F, Cl, CF₃ or Br;

A is O or S(O)_(n), where n is 0, 1 or 2;

R¹ is H, F, Cl, Br or CH₃ ;

X is CH₃ or OCH₃ ;

Y is CH₃, OCH₃, OCH₂ CH₃, (CH₂)_(m) OCH₃ (where m is 1 or 2), OCH₂ CH₂OCH₃, or OCHR² CO₂ R³, where R² is H or CH₃ and R³ is CH₃ or C₂ H₅ ; and

E is CH or N.

Preferred in order of increasing preference for reasons of increasedactivity or ease of synthesis, or both, are:

(1) Compounds of Formula (I), wherein W is O.

(2) Compounds of preference (1), wherein Y is CH₃ or CH₃ O.

(3) Compounds of preference (2), wherein A is O, S or SO₂.

(4) Compounds of preference (2), wherein R¹ is H or Cl.

(5) Compounds of preference (3), wherein R¹ is H or Cl.

Specifically preferred for their outstanding biological activity or veryfavorable ease of synthesis, or both, are:

5-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(trifluoromethoxy)benzenesulfonamide;

2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-5-(trifluoromethoxy)benzenesulfonamide;

N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide;

N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide;and

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide,

alone or in admixture.

DETAILED DESCRIPTION Synthesis

Since not all of the compounds included within Formula (I) can be madeby the same synthesis scheme, Formula (I) is divided into compoundgroups II and III, synthesis for each of which is discussed separately;compound groups II and III are: ##STR8## wherein the substituents aredefined as for Formula (I).

(Haloalkoxy)benzene derivatives (1) as starting materials forpreparation of II can be made by methods well known in the art.

(Trifluoromethoxy)benzene derivatives can be made by the method ofSheppard [J. Org. Chem. 29, 1 (1964)], e.g.: ##STR9##

(Tetrahaloethoxy)benzene derivatives can be made by the method ofEngland et al. [J. Am. Chem. Soc. 82, 5116 (1960)], which also appliesto the hexafluoropropoxy compounds, e.g. ##STR10##

The latter compound can be purchased from Fairfield Chemical Co.,Blythewood, S.C.

(Trifluoroethoxy)benzene derivatives can be made by reaction oftrifluoroethanol with an activated aromatic halide, e.g.: ##STR11##

In reaction (a) sodium hydride and trifluoroethanol are mixed in anaprotic solvent, such as dimethylformamide (DMF), dioxane ortetrahydrofuran (THF), with 2-(fluoro or chloro)-1-nitrobenzene. Thereaction proceeds to completion at ambient temperature. Heat may beapplied (e.g., with a steam bath) if desired to speed the reaction tocompletion. The product is isolated by diluting the reaction mixturewith water, extracting with an organic water-immiscible solvent andevaporation of the solvent. This reaction is similar to that describedin Japanese Pat. No. 5 2057-320.

(Difluoromethoxy)benzene derivatives can be made by the method ofYagupolskii et al. [Chem. Abstr. 70, 96318d (1969)]e.g.: ##STR12##

Preparation of compound II is shown schematically, first for the casewherein R is CF₃ or CF₃ CH₂ : ##STR13##

Chlorosulfonation of aromatic substrates is well known (e.g., L. F.Fieser and M. Fieser, "Advanced Organic Chemistry", 696-698, Reinhold,N.Y., 1961). The chlorosulfonation can be accomplished by addition ofthe trifluoromethoxy compound to the chlorosulfonic acid or vice versa,optionally in the presence of a cosolvent, such as an alkane orchlorinated alkane (e.g., hexane, 1-chlorobutane, methylene chloride,etc.). The reaction temperature is not critical, with a range of about-5° to 50° operable and ambient temperature (e.g. 20° to 30°) preferred,for convenience. At ambient temperature some hydrolysis of thetrifluoromethoxy group occurs. At lower temperatures, chlorosulfonationoccurs more slowly with less of the hydrolysis, while at highertemperatures, chlorosulfonation occurs more rapidly with moreaccompanying hydrolysis. Reaction time at ambient temperature is about 1to 24 hours, depending on the exact substrate being chlorosulfonated,with an overnight period (about 16 hours) satisfactory.Chlorosulfonation of the tetrahaloethoxy, hexafluoropropoxy anddifluoromethoxy compounds is more difficult to control withouthydrolysis of the haloalkoxy group than is chlorosulfonation of thetrifluoromethoxy or trifluoroethoxy compounds.

The aromatic sulfonyl chloride is conveniently isolated from thereaction mixture by pouring the mixture into ice water, followed byextraction with a water-immiscible organic solvent in which the aromaticsulfonyl chloride is soluble. Such solvents include 1-chlorobutane,methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene anddiethyl ether. The solution of the sulfonyl chloride can be dried andevaporated to provide the sulfonyl chloride, which can be furtherpurified by distillation, preferably in vacuum to suppress any thermallydependent decomposition. Alternatively, the solution of the sulfonylchloride can be used directly in reaction with ammonia in the next step,preparation of the sulfonamide.

Chlorosulfonation of 1 can produce isomeric mixtures, e.g.: ##STR14##

Such isomeric mixtures can be separated by conventional routes (e.g.,fractional distillation, chromatography) or used without separation. Inthe latter case, isomeric mixtures of sulfonamides, sulfonyl isocyanatesand thiocyanates, sulfonylureas and sulfonylthioureas are formed in thesubsequent reactions. Similarly, the isomeric mixtures of intermediatesformed further in the synthesis sequence can be separated or used asisomeric mixtures; isomeric mixtures of product sulfonyl (ureas andthioureas) can be used as herbicides or separated and used as individualcompounds. ##STR15##

Conversion of sulfonyl chlorides to sulfonamides is well known (e.g., L.Fieser and M. Fieser, op. cit., 699). It is convenient to dissolve thesulfonyl chloride 2a in an inert solvent, e.g. toluene, ethyl acetate,tetrahydrofuran, etc., and sparge in gaseous ammonia until the formationof ammonium chloride (insoluble in the solvent) ceases. Temperature isnot critical and can range from about -20° to the boiling point of thesolvent. For convenience, ambient temperatures are preferred.

The product can be isolated from the reaction mixture by evaporation andtreatment of the residue with water to remove ammonium chloride. If theproduct precipitates during reaction it can be removed by filtration ofthe reaction mixture and washing with water. If the product remains insolution in the reaction mixture and the solvent is water-immiscible,the mixture can be washed with water and the product obtained byevaporation of the solvent. If the product remains in solution in thereaction mixture and the solvent is water-miscible, the product can beprecipitated by addition of water, then recovered by filtration.##STR16##

The sulfonamide 3 is converted to the sulfonyl isocyanate or sulfonylisothiocyanate 4.

Sulfonyl isocyanates can be made by the method of Ulrich et al. [J. Org.Chem. 34, 3200 (1969)]: ##STR17##

The sulfonamide is boiled under reflux with an excess of thionylchloride, which functions as a reactant and solvent. The reaction iscontinued until the sulfonamide protons are undectable in the protonresonance spectrum. An overnight reaction period (about 16 hours) isgenerally sufficient. The thionyl chloride is evaporated and the residuedissolved in an inert solvent, such as toluene, benzene, xylene, etc.,treated with a catalytic amount of pyridine, then with at least oneequivalent of phosgene. The mixture is heated to about 60°-140°, with80°-100° preferred. Conversion to the isocyanate is substantiallycomplete within about 1/4 to 3 hours. The mixture containing thesulfonyl isocyanate can be used directly for the next reaction step(formation of sulfonylurea) or the sulfonyl isocyanate can be isolatedin purified form by filtration and evaporation of the filtrate,optionally followed by vacuum distillation.

Sulfonyl isocyanates can also be made by mixing the sulfonamide, analkyl isocyanate (e.g. butyl isocyanate) and a catalytic amount of1,4-diaza[2.2.2]-bicyclooctane (DABCO) in xylene or other inert solventof sufficiently high boiling point (e.g. >135°), heating to about 135°,and adding phosgene until an excess is present (indicated by a drop inboiling point). The mixture is further heated and excess phosgene drivenoff. After the mixture is cooled and filtered from insoluble material,the solvent, alkyl isocyanate and excess phosgene are evaporated,leaving the crude sulfonyl isocyanate, optionally purified further byvacuum distillation.

Sulfonyl isothiocyanates can be made by the method of Hartke [Chem.Abstr. 64, 15783e (1966)]: ##STR18##

The sulfonamide in dimethylformamide (DMF) is treated with an equivalentof carbon disulfide and 2 equivalents of powdered potassium hydroxide atabout 35°. The mixture is stirred (about 1-8 hours) until solution issubstantially complete, then diluted with an aprotic solvent, such asethyl acetate, to precipitate the intermediate dipotassium salt shown.The latter is separated by filtration from the reaction mixture,suspended in an inert solvent, such as toluene, and treated with 2 molesof phosgene (or thionyl chloride, etc.) at about 0°. The mixture isallowed to warm to ambient temperature, filtered, and the sulfonylisothiocyanate used in solution for the next reaction step (formation ofsulfonylthiourea) or isolated by evaporation of solvent. The sulfonylisothiocyanates may dimerize or trimerize in some cases, but the dimersand trimers still function to provide the sulfonylthioureas in the nextreaction step (No. 4). ##STR19##

The sulfonyl isocyanate or isothiocyanate 4 reacts with theaminoheterocycle 5 to provide the (trifluoromethoxy ortrifluoroethoxy)benzenesulfonyl(urea or thiourea) II (with R=CF₃ or CF₃CH₂). This reaction is best carried out in inert organic solvent, suchas acetonitrile, tetrahydrofuran, methylene chloride, etc. The reactionis generally exothermic. Conveniently, the starting reaction temperatureis ambient, but can be varied from about 0° to 100° if desired. Theproduct can be isolated by filtration if it precipitates from thereaction mixture, otherwise the solvent can be evaporated and theresidual product obtained thereby, with optional further purficationobtained by trituration with an organic solvent (e.g., diethyl ether,1-chlorobutane, etc.) in which it is only sparingly soluble. ##STR20##

Reaction 5 represents an alternative method for preparation ofsulfonylthioureas. The sulfonamide 3 reacts with the heterocyclicisothiocyanate 6 to form the sulfonylthiourea II (with W=S and R=CF₃ orCF₃ CH₂). The heterocyclic isothiocyanates 6 used in this procedure canbe made, for example, by the method of Japan patent application Pub:Kokai 51-143686, June 5, 1976, or that of W. Abraham and G. Barnikow,Tetrahedron 29, 691 (1973). Reaction 5 is carried out in an inert polarsolvent such as acetone or methyl ethyl ketone, at 20° to 50°, in thepresence of a basic catalyst such as potassium carbonate or sodiumcarbonate, in about 1 to 10 hours. The alkali metal salt of thesulfonylthiourea is filtered off, suspended in water, and the pHadjusted down to 1-3 with mineral acid (e.g. hydrochloric acid) to formthe product sulfonylthiourea, which is recovered by filtration.

As an alternative to reaction 1, the sulfonyl chloride can be made fromthe corresponding aniline compound 7 by diazotization, then treatmentwith sulfur dioxide and cuprous chloride. It should be emphasized thatwhereas reaction 1, is written as applicable to compounds where R=CF₃ orCF₃ CH₂ (i.e., to trifluoromethoxy or trifluoroethoxy compounds),reaction 6 is applicable to compounds where R=CF₃, CH₂ CF₃, ortetrahaloethyl, CHF₂ or hexafluoropropyl; thus reaction 6 is of moregeneral applicability than reaction 1. ##STR21##

Compound 7, where R is CF₃, tetrahaloethyl, HCF₂ or hexafluoropropyl canbe produced by methods described by Sheppard (loc. cit.), England (loc.cit.) and Yagupolskii (loc. cit.). The aniline compound 7 is diazotizedaccording to methods well known in the art, such as the addition ofsodium nitrite to a hydrochloric acid solution of the compound 7. Theintermediate diazonium compound is added, as in the well knownSandmeyer-type reaction, to a mixture of cuprous chloride, sulfurdioxide, and acetic acid at reduced temperature, e.g. 0° to 20°. Themixture is kept cold for 1/4 to 2 hours, then is allowed to warm toambient temperature and continue to react until nitrogen evolution hassubstantially stopped. Dilution with water precipitates the sulfonylchloride, generally as an oil, which is extracted into awater-immiscible organic solvent, e.g. 1-chlorobutane, diethyl ether,toluene, ethyl acetate and the like. The organic extract can be driedand evaporated to the sulfonyl chloride or the solution can be useddirectly in the next step (sulfonamide preparation).

The sulfonyl chloride 2b can be used in the same sequential manner assulfonyl chloride 2a to produce the corresponding sulfonamides, sulfonylisocyanates and isothiocyanates, sulfonylureas, and sulfonylthioureas.

When a nitration reaction is used to make the precursor to 7, in somecases isomeric mixtures are formed, e.g.: ##STR22##

The resulting isomeric mixtures can be separated by conventional means(e.g., fractional distillation or chromatography), or used as such; inthe latter case isomeric mixtures of the aniline 7, sulfonyl chloride,sulfonamide, sulfonyl isocyanate and isothiocyanate, sulfonylurea andsulfonylthiourea are found in the reactions which follow. Likewise, theisomeric mixtures of intermediates further in the synthesis sequence canbe separated or used as the isomeric mixtures; and isomeric mixtures ofproduct sulfonyl(ureas and thioureas) can be used as herbicides orseparated and so used.

(Haloalkylthio, haloalkylsulfinyl andhaloalkyl(sulfonyl)benzenesulfonylureas ##STR23## wherein thesubstituents are defined as for compound (I).

(Haloalkylthio, haloalkylsulfinyl and haloalkylsulfonyl)benzenederivatives 8a and 8b as starting materials for preparation of III, canbe made by known methods [e.g. Chem. Abstr. 70, 96324c (1969); Chem.Abstr. 72, 66651f (1970); England, loc. cit.; Yagupolskii, loc. cit.].

The (trifluoroethylthio)benzenes can be made by reaction of thethiophenol compounds with a trifluoroethylating agent, such astrifluoroethyl iodide or trifluoroethyl trichloromethanesulfonate. Thethiophenol compound is reacted with powdered potassium hydroxide andtrifluoroethyl iodide in an aprotic solvent such as DMF, dioxane or THF.The reaction proceeds to completion at ambient temperature. Heat (e.g.,with a steam bath) may be applied to increase the reaction rate. Theproduct is isolated as described in reaction (a). ##STR24##

Chlorosulfonation of 8a proceeds in the same manner as described forreaction 1 for the oxygen analog 1. ##STR25##

Conversion of the sulfonyl chloride sequentially to the amide, theisocyanate of isothiocyanate, and the sulfonylurea or sulfonylthiourea,proceeds as described for the oxygen analogs in reactions 2, 3, 4 and 5.##STR26##

The nitration is conveniently carried out by slow addition of slightlymore than 1 equivalent of 90% nitric acid to a stirred, cooled (10°-30°)mixture of the sulfide 8b in sulfuric acid, stirring for an additional10-45 minutes, pouring the reaction mixture into ice water, extractingthe nitro compound into a water-immiscible organic solvent (e.g.,1-chlorobutane or methylene chloride), and evaporating the solution toleave residual nitro compound, which may be further purified by vacuumdistillation. Thus, the reaction is a simple mononitration of asubstituted benzene ring, a reaction well known in the art.

As mentioned for the oxygen analog, nitration of 8b can lead to isomericnitro compounds which, likewise, can be separated or used as such.##STR27##

The sulfide 10 is oxidized to the sulfoxide (e.g. with 20-30% H₂ O₂ inacetic acid, 1-2 hours at 90°-100°); or the sulfide 10 is oxidized tothe sulfone [e.g. with chromium trioxide in acetic acid at 90°-110°during 1/2-2 hours]. See Chem. Abstr. 70, 96324c (1969). If no oxidizingagent is used, n remains at zero and 10≡11. ##STR28##

Reduction of nitrobenzene derivatives to nitroaniline derivatives iswell known in the art [e.g., W. J. Hickinbottom, "Reactions of OrganicCompounds," 452-459, Longmans, London, 1959]. For example, the reductioncan be accomplished by the portionwise addition of powdered iron to amixture of the nitro compound in aqueous acetic acid at 60°-110°;followed by dilution of the reaction mixture with water and filteringoff, extracting or, when n=0, steam-distilling the aniline product.Aminothiophenols can be directly tetrahaloethylated orhexafluoropropylated on the chalcogen with tetrahaloethylene orhexafluoropropene to provide directly compounds 12 with n=0 (England etal., loc. cit.; Chem. Abstr. 73, 36584q). Also, compound 12a iscommercially available (Aldrich Chemical Co., Milwaukee, Wisc.):##STR29##

The aniline derivative 12 is diazotized and converted to the sulfonylchloride, sulfonamide, sulfonyl isocyanate or isothiocyanate andsulfonylurea or sulfonylthiourea as described for reactions 6 and 2through 5. ##STR30##

As an alternate method for preparation of the intermediate nitrosulfone(11a), the sulfide 8b is oxidized, as described for reaction 10, to thesulfone 13, followed by nitration to the nitrosulfone 11a. Nitration isaccomplished with 90% nitric acid in 20% oleum at 90°-100°, the nitrogroup joining the ring meta to the haloalkylsulfonyl group [Chem. Abstr.53, 21766a (1959)]. The nitrosulfone 11a is converted to thesulfonylurea or sulfonylthiourea as already described (Reactions 11, 6and 2 through 5).

Exemplary compounds within structure (I) that can be made by one or moreof the described methods are listed in Table I. Structure IV, as definedbelow, represents compounds useful as intermediates to compounds ofstructure (I). Exemplary compounds within structure IV that can be madeby one or more of the described methods are listed in Table II.##STR31## wherein the substituents R, A and R¹ are defined as forFormula (I), and L is Cl, NH₂, --NCO or --NCS. These lists are not to beconsidered as limiting, but merely exemplary.

                                      TABLE I                                     __________________________________________________________________________     ##STR32##                               (I)                                  RA        R.sup.1                                                                           W E  X   Y           m.p.                                       __________________________________________________________________________    2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-HCF.sub.2 CF.sub.2 O                                                                  5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-HCF.sub.2 CF.sub.2 O                                                                  2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                                                  173-177°                            2-HCFClCF.sub.2 O                                                                       5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-HCFClCF.sub.2 O                                                                       2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-HCFBrCF.sub.2 O                                                                       5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                                                  171-172° (dec)                      5-HCFBrCF.sub.2 O                                                                       2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 CH.sub.2 O                                                                   5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 CH.sub.2 O                                                                   2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 O                                                                            5-Br                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-Br                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 O                                                                            5-F O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-F O CH CH.sub.3                                                                          CH.sub.3                                               2-HCF.sub.2 CF.sub.2 O                                                                  5-CH.sub.3                                                                        O CH CH.sub.3                                                                          CH.sub.3                                               5-HCF.sub.2 CF.sub.2 O                                                                  2-CH.sub.3                                                                        O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 O                                                                            5-Cl                                                                              S CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-Cl                                                                              S CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 O                                                                            5-Cl                                                                              S N  OCH.sub.3                                                                         OCH.sub.3                                              5-CF.sub.3 O                                                                            2-Cl                                                                              S N  OCH.sub.3                                                                         OCH.sub.3                                              3-CF.sub.3 O                                                                            H   O CH CH.sub.3                                                                          CH.sub.3                                               6-CF.sub.2 HCF.sub.2 O                                                                  2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.2 HCF.sub.2 O                                                                  H   O CH CH.sub.3                                                                          CH.sub.3    190-193°                            2-CF.sub.2 HCF.sub. 2 O                                                                 H   O N  OCH.sub.3                                                                         CH.sub.3    180-183°                            2-CF.sub.2 HCF.sub.2 O                                                                  H   O CH OCH.sub.3                                                                         OCH.sub.3   172-175°                            2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.3                                              5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.3                                              2-CF.sub.3 O                                                                            5-Cl                                                                              O CH OCH.sub.3                                                                         OCH.sub.3                                              5-CF.sub.3 O                                                                            2-Cl                                                                              O CH OCH.sub.3                                                                         OCH.sub.3                                              2-CF.sub.3 O                                                                            5-Cl                                                                              O CH OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                     5-CF.sub.3 O                                                                            2-Cl                                                                              O CH OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                     2-CF.sub.3 O                                                                            5-Cl                                                                              O CH OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.3                            5-CF.sub.3 O                                                                            2-Cl                                                                              O CH OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.3                            2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                            5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                            2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 CH.sub.3                          5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 CH.sub.3                          2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 C.sub.2 H.sub.5                   5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 C.sub.2 H.sub.5                   2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OMe                                 5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OMe                                 2-CF.sub.3 O                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          OC.sub.2 H.sub.5                                       5-CF.sub.3 O                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          OC.sub.2 H.sub.5                                       2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.3                                              5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.3                                              2-CF.sub.3 O                                                                            5-Cl                                                                              O N  OCH.sub.3                                                                         OCH.sub.3                                              5-CF.sub.3 O                                                                            2-Cl                                                                              O N  OCH.sub.3                                                                         OCH.sub.3                                              2-CF.sub.3 O                                                                            5-Cl                                                                              O N  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                     5-CF.sub.3 O                                                                            2-Cl                                                                              O N  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                     2-CF.sub.3 O                                                                            5-Cl                                                                              O N  OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.3                            2-CF.sub.3 CH.sub.2 O                                                                   H   O CH CH.sub.3                                                                          CH.sub. 3   203-205° (dec)                      2-HCFClCF.sub.2 O                                                                       H   O CH CH.sub.3                                                                          CH.sub.3                                               2-HCFBrCF.sub.2 O                                                                       H   O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 O                                                                            2-Cl                                                                              O N  OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.3                            2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                            5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                            2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                     2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 CH.sub.3                          5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 CH.sub.3                          2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 C.sub.2 H.sub.5                   5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCHCH.sub.3 CO.sub.2 C.sub.2 H.sub.5                   2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                           5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                           2-CF.sub.3 O                                                                            5-Cl                                                                              O N  CH.sub.3                                                                          OC.sub.2 H.sub.5                                       5-CF.sub.3 O                                                                            2-Cl                                                                              O N  CH.sub.3                                                                          OC.sub.2 H.sub.5                                       2-CF.sub.3 S                                                                            5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 S                                                                            2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                ##STR33##                                                                              5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                ##STR34##                                                                              2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               5-CF.sub.3 SO.sub.2                                                                     2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               3-CF.sub.3 SO.sub.2                                                                     H   O CH CH.sub.3                                                                          CH.sub.3                                                ##STR35##                                                                              H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 SO.sub.2                                                                     H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 S                                                                            H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.2 HCF.sub.2 S                                                                  H   O CH CH.sub.3                                                                          CH.sub.3    196° (dec)                          2-CFClHCF.sub.2 S                                                                       H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CFBrHCF.sub.2 S                                                                       H   O CH CH.sub.3                                                                          CH.sub.3                                                ##STR36##                                                                              H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.2 HCF.sub.2 SO.sub.2                                                           H   O CH CH.sub.3                                                                          CH.sub.3                                               2-HCF.sub.2 O                                                                           H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub. 3 CHFCF.sub.2 O                                                               H   O CH CH.sub.3                                                                          CH.sub.3    177-178°                            2-CF.sub.3 CHFCF.sub.2 O                                                                H   O N  OCH.sub.3                                                                         CH.sub.3    154-157°                            2-CF.sub.3 CHFCF.sub.2 O                                                                H   O CH OCH.sub.3                                                                         OCH.sub.3   189°                                2-CF.sub.3 CHFCF.sub.2 O                                                                H   O CH OCH.sub.3                                                                         CH.sub.3    169-170°                            2-HCFBrCF.sub.2 O                                                                       5-Br                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                                                  181-183° (dec)                      5-HCFBrCF.sub.2 O                                                                       2-Br                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.2 HCF.sub.2 S                                                                  5-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                                                                  191-193° (dec)                      5-CF.sub.2 HCF.sub.2 S                                                                  2-Cl                                                                              O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.2 HCF.sub.2 O                                                                  6-CH.sub.3                                                                        O CH CH.sub.3                                                                          CH.sub.3    198° (dec)                          2-CHF.sub.2 S                                                                           H   O CH CH.sub.3                                                                          CH.sub.3                                                ##STR37##                                                                              H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CHF.sub.2 SO.sub.2                                                                    H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 CHFCF.sub.2 S                                                                H   O CH CH.sub.3                                                                          CH.sub.3                                                ##STR38##                                                                              H   O CH CH.sub.3                                                                          CH.sub.3                                               2-CF.sub.3 CHFCF.sub.2 SO.sub.2                                                         H   O CH CH.sub.3                                                                          CH.sub.3                                               2-HCF.sub.2 O                                                                           H   O CH OCH.sub.3                                                                         OCH.sub.3   167-168.5°                          __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                         ##STR39##                     IV                                             RA           R.sup.1  L                                                       ______________________________________                                        2-CF.sub.3 O 5-Cl     Cl                                                      5-CF.sub.3 O 2-Cl     Cl                                                      2-HCF.sub.2 CF.sub.2 O                                                                     5-Cl     Cl                                                      5-HCF.sub.2 CF.sub.2 O                                                                     2-Cl     Cl                                                      2-HCFClCF.sub.2 O                                                                          5-Cl     Cl                                                                                          oil                                       5-HCFClCF.sub.2 O                                                                          2-Cl     Cl                                                      2-HCFBrCF.sub.2 O                                                                          5-Cl     Cl                                                                                          oil                                       5-HCFBrCF.sub.2 O                                                                          2-Cl     Cl                                                      2-CF.sub.3 CH.sub.2 O                                                                      5-Cl     Cl                                                      5-CF.sub.3 CH.sub.2 O                                                                      2-Cl     Cl                                                      2-CF.sub.3 O 5-Br     Cl                                                      5-CF.sub.3 O 2-Br     Cl                                                      2-CF.sub.3 O 5-F      Cl                                                      5-CF.sub.3 O 2-F      Cl                                                      2-HCF.sub.2 CF.sub.2 O                                                                     5-CH.sub.3                                                                             Cl                                                      5-HCF.sub.2 CF.sub.2 O                                                                     2-CH.sub.3                                                                             Cl                                                      2-CF.sub.2 HCF.sub.2 O                                                                     H        Cl                                                      2-CF.sub.3 CH.sub.2 O                                                                      H        Cl            solid                                     2-HCFClCF.sub.2 O                                                                          H        Cl                                                      2-HCFBrCF.sub.2 O                                                                          H        Cl                                                      2-CF.sub.3 S 5-Cl     Cl                                                      5-CF.sub.3 S 2-Cl     Cl                                                       ##STR40##   5-Cl     Cl                                                       ##STR41##   2-Cl     Cl                                                      5-CF.sub.3 SO.sub.2                                                                        2-Cl     Cl                                                      2-CF.sub.3 S H        Cl                                                       ##STR42##   H        Cl                                                      2-CF.sub.3 SO.sub.2                                                                        H        Cl                                                      2-HCF.sub.2 CF.sub.2 S                                                                     H        Cl                                                       ##STR43##   H        Cl                                                      2-HCF.sub.2 CF.sub.2 SO.sub.2                                                              H        Cl                                                      2-HCFClCF.sub.2 S                                                                          H        Cl                                                      2-HCFBrCF.sub.2 S                                                                          H        Cl                                                      2-HCF.sub.2 CF.sub.2 S                                                                     5-Cl     Cl                                                                                          oil                                       5-HCF.sub.2 CF.sub.2 S                                                                     2-Cl     Cl                                                      2-HCF.sub.2 O                                                                              H        Cl            oil                                       2-CF.sub.3 CHFCF.sub.2 O                                                                   H        Cl            oil                                       2-HCF.sub.2 S                                                                              H        Cl                                                       ##STR44##   H        Cl                                                      2-HCF.sub.2 SO.sub.2                                                                       H        Cl                                                      2-CF.sub.3 CHFCF.sub.2 S                                                                   H        Cl                                                       ##STR45##   H        Cl                                                      2-CF.sub.3 CHFCF.sub.2 SO.sub.2                                                            H        Cl                                                      2-HCF.sub.2 CF.sub.2 O                                                                     5-Br     Cl            oil, bp                                                                        83-103/0.1                               5-HCF.sub.2 CF.sub.2 O                                                                     2-Br     Cl            Torr                                      2-HCF.sub.2 CF.sub.2 O                                                                     6-CH.sub.3                                                                             Cl            oil                                       2-CF.sub.3 O 5-Cl     NH.sub.2                                                5-CF.sub.3 O 2-Cl     NH.sub.2                                                2-HCF.sub.2 CF.sub.2 O                                                                     5-Cl     NH.sub.2                                                5-HCF.sub.2 CF.sub.2 O                                                                     2-Cl     NH.sub.2                                                2-HCFClCF.sub.2 O                                                                          5-Cl     NH.sub.2                                                                                    124-126°                           5-HCFClCF.sub.2 O                                                                          2-Cl     NH.sub.2                                                2-HCFBrCF.sub.2 O                                                                          5-Cl     NH.sub.2                                                                                     86-90° and                        5-HCFBrCF.sub.2 O                                                                          2-Cl     NH.sub.2      101-103°                           2-CF.sub.3 CH.sub.2 O                                                                      5-Cl     NH.sub.2                                                5-CF.sub.3 CH.sub.2 O                                                                      2-Cl     NH.sub.2                                                2-CF.sub.3 O 5-Br     NH.sub.2                                                5-CF.sub.3 O 2-Br     NH.sub.2                                                2-CF.sub.3 O 5-F      NH.sub.2                                                5-CF.sub.3 O 2-F      NH.sub.2                                                2-HCF.sub.2 CF.sub.2 O                                                                     5-CH.sub.3                                                                             NH.sub.2                                                5-HCF.sub.2 CF.sub.2 O                                                                     2-CH.sub.3                                                                             NH.sub.2                                                2-CF.sub.2 HCF.sub.2 O                                                                     H        NH.sub.2      118-120°                           2-CF.sub.3 CH.sub.2 O                                                                      H        NH.sub.2      127-129°                           2-HCFClCF.sub.2 O                                                                          H        NH.sub.2                                                2-HCFBrCF.sub.2 O                                                                          H        NH.sub.2                                                2-CF.sub.3 S 5-Cl     NH.sub.2                                                5-CF.sub.3 S 2-Cl     NH.sub.2                                                 ##STR46##   5-Cl     NH.sub.2                                                 ##STR47##   2-Cl     NH.sub.2                                                5-CF.sub.3 SO.sub.2                                                                        2-Cl     NH.sub.2                                                2-CF.sub.3 S H        NH.sub.2                                                 ##STR48##   H        NH.sub.2                                                2-CF.sub.3 SO.sub.2                                                                        H        NH.sub.2                                                2-HCF.sub.2 CF.sub.2 S                                                                     H        NH.sub.2                                                 ##STR49##   H        NH.sub.2                                                2-HCF.sub.2 CF.sub.2 SO.sub.2                                                              H        NH.sub.2                                                2-HCFClCF.sub.2 S                                                                          H        NH.sub.2       99-101°                           2-HCFBrCF.sub.2 S                                                                          H        NH.sub.2                                                2-HCF.sub.2 CF.sub.2 S                                                                     5-Cl     NH.sub.2                                                                                     96-100°                           5-HCF.sub.2 CF.sub.2 S                                                                     2-Cl     NH.sub.2                                                2-HCF.sub.2 O                                                                              H        NH.sub.2      130-134°                           2-CF.sub.3 CHFCF.sub.2 O                                                                   H        NH.sub.2       94-96°                            2-HCF.sub.2 S                                                                              H        NH.sub.2                                                 ##STR50##   H        NH.sub.2                                                2-HCF.sub.2 SO.sub.2                                                                       H        NH.sub.2                                                2-CF.sub.3 CHFCF.sub.2 S                                                                   H        NH.sub.2                                                 ##STR51##   H        NH.sub.2                                                2-CF.sub.3 CHFCF.sub.2 SO.sub.2                                                            H        NH.sub.2                                                2-HCF.sub.2 CF.sub.2 O                                                                     5-Br     NH.sub.2                                                                                     99-117°                           5-HCF.sub.2 CF.sub.2 O                                                                     2-Br     NH.sub.2                                                2-HCF.sub.2 CF.sub.2 O                                                                     6-CH.sub.3                                                                             NH.sub.2      104-105°                           2-CF.sub.3 O 5-Cl     NCO                                                     5-CF.sub.3 O 2-Cl     NCO                                                     2-HCF.sub.2 CF.sub.2 O                                                                     5-Cl     NCO                                                     5-HCF.sub.2 CF.sub.2 O                                                                     2-Cl     NCO                                                     2-HCFClCF.sub.2 O                                                                          5-Cl     NCO                                                                                         oil                                       5-HCFClCF.sub.2 O                                                                          2-Cl     NCO                                                     2-HCFBrCF.sub.2 O                                                                          5-Cl     NCO                                                                                         oil                                       5-HCFBrCF.sub.2 O                                                                          2-Cl     NCO                                                     2-CF.sub.3 CH.sub.2 O                                                                      5-Cl     NCO                                                     5-CF.sub.3 CH.sub.2 O                                                                      2-Cl     NCO                                                     2-CF.sub.3 O 5-Br     NCO                                                     5-CF.sub.3 O 2-Br     NCO                                                     2-CF.sub.3 O 5-F      NCO                                                     5-CF.sub.3 O 2-F      NCO                                                     2-HCF.sub.2 CF.sub.2 O                                                                     5-CH.sub.3                                                                             NCO                                                     5-HCF.sub.2 CF.sub.2 O                                                                     2-CH.sub.3                                                                             NCO                                                     2-CF.sub.2 HCF.sub.2 O                                                                     H        NCO                                                     2-CF.sub.3 CH.sub.2 O                                                                      H        NCO           oil                                       2-HCFClCF.sub.2 O                                                                          H        NCO                                                     2-HCFBrCF.sub.2 O                                                                          H        NCO                                                     2-CF.sub.3 S 5-Cl     NCO                                                     5-CF.sub.3 S 2-Cl     NCO                                                      ##STR52##   5-Cl     NCO                                                      ##STR53##   2-Cl     NCO                                                     5-CF.sub.3 SO.sub.2                                                                        2-Cl     NCO                                                     2-CF.sub.3 S H        NCO                                                      ##STR54##   H        NCO                                                     2-CF.sub.3 SO.sub.2                                                                        H        NCO                                                     2-HCF.sub.2 CF.sub.2 S                                                                     H        NCO                                                      ##STR55##   H        NCO                                                     2-HCF.sub.2 CF.sub.2 SO.sub.2                                                              H        NCO                                                     2-HCFClCF.sub.2 S                                                                          H        NCO           oil                                       2-HCFBrCF.sub.2 S                                                                          H        NCO                                                     2-HCF.sub.2 CF.sub.2 O                                                                     5-Br     NCO                                                                                         oil                                       5-HCF.sub.2 CF.sub.2 O                                                                     2-Br     NCO                                                     2-HCF.sub.2 O                                                                              H        NCO           oil                                       2-CF.sub.3 CHFCF.sub.2 O                                                                   H        NCO           oil                                       2-HCF.sub.2 S                                                                              H        NCO                                                      ##STR56##   H        NCO                                                     2-HCF.sub.2 SO.sub.2                                                                       H        NCO                                                     2-CF.sub.3 CHFCF.sub.2 S                                                                   H        NCO                                                      ##STR57##   H        NCO                                                     2-CF.sub.3 CHFCF.sub.2 SO.sub.2                                                            H        NCO                                                     2-HCF.sub.2 CF.sub.2 S                                                                     5-Cl     NCO                                                                                         oil                                       5-HCF.sub.2 CF.sub.2 S                                                                     2-Cl     NCO                                                     2-HCF.sub.2 CF.sub.2 O                                                                     6-CH.sub.3                                                                             NCO           oil                                       2-CF.sub.3 O 5-Cl     NCS                                                     5-CF.sub.3 O 2-Cl     NCS                                                     2-HCF.sub.2 CF.sub.2 O                                                                     5-Cl     NCS                                                     5-HCF.sub.2 CF.sub.2 O                                                                     2-Cl     NCS                                                     2-HCFClCF.sub.2 O                                                                          5-Cl     NCS                                                     5-HCFClCF.sub.2 O                                                                          2-Cl     NCS                                                     2-HCFBrCF.sub.2 O                                                                          5-Cl     NCS                                                     5-HCFBrCF.sub.2 O                                                                          2-Cl     NCS                                                     2-CF.sub.3 CH.sub.2 O                                                                      5-Cl     NCS                                                     5-CF.sub.3 CH.sub.2 O                                                                      2-Cl     NCS                                                     2-CF.sub.3 O 5-Br     NCS                                                     5-CF.sub.3 O 2-Br     NCS                                                     2-CF.sub.3 O 5-F      NCS                                                     5-CF.sub.3 O 2-F      NCS                                                     2-HCF.sub.2 CF.sub.2 O                                                                     5-CH.sub.3                                                                             NCS                                                     5-HCF.sub.2 CF.sub.2 O                                                                     2-CH.sub.3                                                                             NCS                                                     2-CF.sub.2 HCF.sub.2 O                                                                     H        NCS                                                     2-CF.sub.3 CH.sub.2 O                                                                      H        NCS                                                     2-HCFClCF.sub.2 O                                                                          H        NCS                                                     2-HCFBrCF.sub.2 O                                                                          H        NCS                                                     2-CF.sub.3 S 5-Cl     NCS                                                     5-CF.sub.3 S 2-Cl     NCS                                                      ##STR58##   5-Cl     NCS                                                      ##STR59##   2-Cl     NCS                                                     5-CF.sub.3 SO.sub.2                                                                        2-Cl     NCS                                                     2-CF.sub.3 S H        NCS                                                      ##STR60##   H        NCS                                                     2-CF.sub.3 SO.sub.2                                                                        H        NCS                                                     2-HCF.sub.2 CF.sub.2 S                                                                     H        NCS                                                      ##STR61##   H        NCS                                                     2-HCF.sub.2 CF.sub.2 SO.sub.2                                                              H        NCS                                                     2-HCFClCF.sub.2 S                                                                          H        NCS                                                     2-HCFBrCF.sub.2 S                                                                          H        NCS                                                     2-HCF.sub.2 O                                                                              H        NCS                                                     2-CF.sub.3 CHFCF.sub.2 O                                                                   H        NCS                                                     2-HCF.sub.2 S                                                                              H        NCS                                                      ##STR62##   H        NCS                                                     2-HCF.sub.2 SO.sub.2                                                                       H        NCS                                                     2-CF.sub.3 CHFCF.sub.2 S                                                                   H        NCS                                                      ##STR63##   H        NCS                                                     2-CF.sub.3 CHFCF.sub.2 SO.sub.2                                                            H        NCS                                                     ______________________________________                                    

In the examples which follow, all parts and percentages are by weightand all temperatures in degrees centigrade unless specified otherwise.The examples are not to be considered as limiting, but merely exemplaryof the methods which can be used to prepare the compounds of thisinvention.

EXAMPLE 1 ##STR64## a. Into 49.1 g (0.25 mole) of1-chloro-4-(trifluoromethoxy)benzene was dripped 82 ml (1.25 mole) ofchlorosulfonic acid at 20°-25°. The mixture was stirred for a day, thencooled to -10° and poured slowly onto excess, stirred ice. The mixturewas extracted with butyl chloride and the butyl chloride extracts washedwith water, dilute sodium bicarbonate solution, and saturated brine,dried with MgSO₄, and evaporated in vacuo to an orange oil. Vacuumdistillation of the oil provided the product as an oil, bp 114°-116°/8Torr, starting material and some haloformate by-product. The oil was anisomeric mixture comprising the two isomers: ##STR65## b. A solution of26.5 g of the mixed sulfonyl chlorides in 200 ml of THF was gassed withexcess ammonia at ≦30°, then evaporated and the residue treated withwater and ethyl acetate. The ethyl acetate solution was washed withsaturated brine, dried, concentrated to 50 ml, and diluted with hexaneto provide 20 g (81%) of the product as a white solid, m.p. 93°-96°(partial) and 103°-105° (remainder). The product was an isomeric mixtureof the two isomers: ##STR66## c. To 10 g of the mixed sulfonamides wasadded 70 ml of thionyl chloride and the mixture boiled under reflux for20 hours. The thionyl chloride was stripped and the residual oildissolved in 50 ml of toluene. To the solution was added 0.3 ml ofpyridine and 6 ml of liquid phosgene. The resulting mixture was heatedat 85°-90° for 2 hours under phosgene reflux. The cooled mixture wasfiltered and stripped to a residual oil, which was the mixed-isomersulfonyl isocyanate (IR spectrum: strong absorption at 2240 cm⁻¹). Theoil was dissolved in 100 ml of acetonitrile and reacted with 4.4 g of2-amino-4,6-dimethylpyrimidine. An exothermic reaction ensued, withprecipitation of white solid. After 1.5 hours, the white solid wasfiltered off and washed with acetonitrile and ether, providing the titlesulfonylurea isomeric mixture, m.p. 195°-199° (dec.).

Anal. Calcd. for C₁₄ H₁₂ ClF₃ N₄ O₄ S: C, 39.6; H, 2.8; Cl, 8.3; S, 7.5;Found: C, 39.6; H, 2.9; Cl, 8.2; S, 7.9.

EXAMPLE 2 ##STR67## a. A stirred mixture of 20.9 g of2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide, 10 g of butylisocyanate, 50 mg of 1,4-diazabicyclo[2.2.2]octane and 140 ml of xylenewas boiled under reflux for 0.5 hour. Phosgene gas was then passed intothe system under a dry-ice reflux condenser, causing the reactiontemperature to fall to 120°. Phosgene addition was continued until thereaction temperature would not rise above 120°; at this point, phosgeneaddition was stopped. The reaction temperature was raised to 136° byremoval of the dry-ice condenser and allowing phosgene to escape to ascrubber, then lowered to 25°; the mixture was then filtered. Thefiltrate was evaporated in vacuum to provide2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonyl isocyanate as an oil(strong absorption at 2225 cm⁻¹ in the infrared spectrum, for theisocyanate), which can be further purified by vacuum distillation.

b. Into a stirred solution of the2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonyl isocyanate in 200 ml ofacetonitrile was added 12.3 g of 2-amino-4,6-dimethylpyrimidine and themixture stirred overnight (about 15 hours). The mixture was cooled,diluted with diethyl ether and the solid washed with cold acetonitrileand diethyl ether, then vacuum-dried, providing the title sulfonylureaas a white solid, m.p. 190°-193° (dec.).

EXAMPLE 3 ##STR68##

The mixed-isomer sulfonamide, 27.6 g, obtained in Example 1c, isdissolved in 100 ml of DMF and is treated with 7.6 g of carbon disulfideand 6.6 g of powdered 85% potassium hydroxide. The mixture is stirred atabout 35° until dissolution is completed, and again treated with thesame amount of potassium hydroxide and stirred until dissolution iscompleted. The mixture is treated with excess ethyl acetate, addeddropwise to precipitate the intermediate, which is vacuum-dried.

The intermediate is suspended in toluene and reacted at 5°-10° with 20 gof phosgene. After 2 hours at room temperature, the mixture is filteredand stripped to residual sulfonyl isothiocyanate.

A solution of 14.3 g of sulfonyl isothiocyanate in 100 ml ofacetonitrile is reacted with 6.2 g of 2-amino-4,6-dimethylpyrimidine andthe mixture is stirred overnight. Dilution of the concentrated mixturewith ether provides the title sulfonylthioureas as a solid.

EXAMPLE 4 ##STR69##

A mixture of 5.5 g of the mixed-isomer sulfonamide, is obtained fromexample 1, 4.0 g of 4,6-dimethoxy-2-isothiocyanato-1,3,5-triazine and2.7 g of anhydrous potassium carbonate in 70 ml of acetone is warmed to40° with stirring. After 2 hours, a thick precipitate is formed andstirring is continued for three more hours at ambient temperature. Theprecipitate is removed by filtration, suspended in 150 ml of water,stirred and the pH adjusted to 2 by the addition of hydrochloric acid.

The desired product is removed by filtration, washed with cold water anddried to provide the title product.

EXAMPLE 5 ##STR70## a. A solution of 68.2 g of 1-chloro-(2- and3-nitro)-4-(trifluoromethoxy)benzene [J. Org. Chem. 29, 1 (1964)] in amixture of 229 ml of acetic acid and 57 ml of water was treated at80°-95°, portionwise, with 61 g of powdered iron, an additional 57 ml ofwater being added after half the iron was added. After an additional 30minutes heating on a steam bath, the mixture was diluted with water andthe product isolated by steam distillation, followed by extraction ofthe product into butyl chloride, water-washing the butyl chlorideextract, evaporation and distillation at 75°-79°/10 Torr. Yield: 56 g.The product, an oil, is a mixture of the two isomers: ##STR71## b. Theaniline derivative, 56 g, is added to 200 ml of concentratedhydrochloric acid and 60 ml of acetic acid at 0° during 15 minutes. Thena solution of 26 g of sodium nitrite in 70 ml of water is added at 0 to3° during 45 minutes. After an additional 10 minutes at 0°, the mixtureis poured into a mixture of 285 ml of acetic acid, 7 g of cuprouschloride and 50 ml of sulfur dioxide at 5° over 10 minutes. After 15minutes at 0° to 5°, the mixture is warmed to 25° and kept at 25° for 3hours. The mixture is poured into 1.5 l of water and the sulfonylchloride product is extracted into butyl chloride. The butyl chloridesolution is washed with water, dilute sodium bicarbonate solution, andsaturated brine, then dried (MgSO₄). The butyl chloride solutioncontains the same sulfonyl chlorides described in Example 1a, and can beconverted to sulfonylureas or sulfonylthioureas as previously described.EXAMPLE 6 ##STR72##

Into 53.2 g of 4-chlorophenyl trifluoromethyl sulfide is dripped 82 mlof chlorosulfonic acid at 20°. After a day, the mixture is poured ontoexcess ice and extracted with butyl chloride. The butyl chloride extractis washed with water and dilute sodium bicarbonate, and dried. The driedsolution of isomeric sulfonyl chlorides is converted to the sulfonamidesby gassing with ammonia at 25°, stripping, washing the residue withwater and drying in a vacuum oven. The sulfonamides are converted to thesulfonyl isocyanate as described in Example 1c. The sulfonyl isocyanatesisomeric mixture is dissolved in 100 ml of acetonitrile and treated with6.2 g of 2-amino-4,6-dimethylpyrimidine. The mixture is stirredovernight, diluted with butyl chloride and hexane and the title productfiltered off and dried.

EXAMPLE 7 ##STR73##

To 74 ml of concentrated hydrochloric acid and 22 ml of acetic acid isadded 22.5 g of 2-aminophenyl trifluoromethyl sulfone [Chem. Abstr. 70,96324c (1969)] at 0° over 15 minutes. A solution of 9.6 g of sodiumnitrite in 26 ml of water is added at 0° to 3° over 45 minutes. After anadditional 10 minutes at 0°, the reaction mixture is poured into amixture of 107 ml of acetic acid, 2.6 g of cuprous chloride and 19 ml ofsulfur dioxide at 5° over 10 minutes. The mixture is stirred at 0° to 5°for 1 hour and at 25° for 3 hours, then poured into ice water and thesulfonyl chloride extracted into ether. The ether extracts are washedwith water, sodium bicarbonate solution until basic, saturated brine,and then dried with MgSO.sub. 4.

The ether solution is gassed with ammonia at 20°, then stripped. Theresidue is washed with water and the sulfonamide dried in a vacuum oven.

The sulfonamide is converted to the isocyanate as in Example 1c. Theisocyanate is treated in acetonitrile with 12.3 g of2-amino-4,6-dimethylpyrimidine. After an overnight reaction period, themixture is diluted with butyl chloride to provide the title sulfonylureaas a white solid.

EXAMPLE 8 ##STR74## a. Into a cooled (10°) solution of 55 ml of aceticacid and 180 ml concentrated hydrochloric acid was poured 50 g of2-(1,1,2,2-tetrafluoroethoxy)aniline. The resulting thick mixture wascontacted dropwise at 0° to 5° with a solution of 23.5 g of sodiumnitrite in 62 ml of water, providing an orange solution containingsuspended salt. This diazonium mixture was poured, portionwise, into astirred, cooled (0° to 5°) mixture of 45 ml SO₂ (liquid) in 257 ml ofacetic acid. Gas evolution was noted. The mixture was kept at 0° to 5°for 30 minutes, then treated with 300 ml of 1-chlorobutane and 100 ml ofhexane and heated to 25° during a 20-minute period. After an additionalhour, water was added, the organic layer separated and washed with water(2X) and saturated sodium bicarbonate solution until a basic wash isobtained. The chlorobutane solution was dried over MgSO₄, and thefiltered mixture evaporated in vacuum to 69.5 g of yellow oil,2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonyl chloride.

b. The sulfonyl chloride was dissolved in 250 ml of tetrahydrofuran(THF) and contacted at ≦30° with 14.1 ml of ammonia (liquid). After 10minutes, the THF was evaporated in vacuum and the residual solid treatedwith water, and the crude sulfonamide filtered off. The sulfonamide wasrecrystallized from dimethylformamide/water, then 1-chlorobutane/hexane,providing 41.8 g of 2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide as awhite solid, m.p. 117°-119°. An additional portion of product wasrecovered from the mother liquor.

c. The 41.8 g of sulfonamide was mixed with 200 ml of thionyl chlorideand the mixture boiled under reflux for 22.5 hours. The yellow solutionwas evaporated in vacuum and the semisolid residue treated with 150 mlof a solution of phosgene (about 15%) in toluene. Five drops of pyridinewas added and the mixture heated under a dry-ice reflux condenser;phosgene was allowed to escape to a trap until the reaction temperaturereached 85°. After 2 hours at 85°, the mixture was evaporated in vacuumto a residual orange oil and small amounts of solid. The residue wascontacted with 1-chlorobutane, the mixture filtered and the filtrateevaporated in vacuum to an orange oil,2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonyl isocyanate. The isocyanatewas dissolved in 200 ml of acetonitrile and contacted with 23.7 g of2-amino-4,6-dimethoxypyrimidine. A dark coloration immediately ensued,followed by precipitation of solid. After 15 minutes, the mixture wascooled in an ice bath and the solid filtered off. Recrystallization ofthe solid provided 24.3 g of the title compound as a white solid, m.p.191°-192°. An additional 6.6 g of the compound, m.p. 189°-190°, wasobtained by dilution of the mother liquor with hexane.

Anal. Calcd. for C₁₅ H₁₄ F₄ N₄ O₆ S: C, 39.6; H, 3.1; N, 12.3; S, 7.1.Found: C, 40.1; H, 3.1; N, 12.2; S, 7.5.

FORMULATIONS

Useful formulations of the compounds of Formula (I) can be prepared inconventional ways. They include dusts, granules, pellets, suspensions,emulsions, wettable powders, emulsifiable concentrates and the like.Many of them can be applied directly. Sprayable formulations can beextended in suitable media and used at spray volumes of from a fewliters per hectare to several hundred liters per hectare. High-strengthcompositions are used primarily as concentrates which are to be dilutedprior to ultimate use. The formulations, broadly, contain about 0.1% to99% by weight of active ingredient(s) and at least one of (a) about 0.1%to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquiddiluent(s). More specifically, they will contain these ingredients inthe approximate proportions set forth in Table III.

                  TABLE III                                                       ______________________________________                                                      Weight Percent*                                                               Active            Sur-                                                        Ingredient                                                                            Diluent(s)                                                                              factant(s)                                    ______________________________________                                        Wettable Powders                                                                              20-90      0-74     1-10                                      Oil Suspensions, Solutions,                                                                    5-50     40-95     0-15                                      Emulsions (including                                                          Emulsifiable Concentrates)                                                    Aqueous Suspensions                                                                           10-50     40-84     1-20                                      Dusts            1-25     70-99     0-5                                       Granules & Pellets                                                                            0.1-95      5-99.9  0-15                                      High-Strength Compositions                                                                    90-99      0-10     0-2                                       ______________________________________                                         *Active ingredient plus at least one of a surfactant or a diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can be present, depending onthe intended use and the physical properties of the compound. Higherratios of surfactant to active ingredient are sometimes desirable, andare achieved by incorporation into the formulation or by tank mixing.

Some typical diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide", 2nd. Ed., Interscience, NewYork, 1950. Solubility under 0.1% is preferred for suspensionconcentrates; solution concentrates are preferably stable against phaseseparation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MCPublishing Corp., Ridgewood, N.J., as well as Sisely and Wood,"Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.,New York, 1964, list surfactants and recommended uses. All formulationscan contain minor amounts of additives to reduce foaming, caking,corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending, and usually grinding, as in a hammer- or fluid-energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be made byspraying the active material on preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147 ff. and "Perry's Chemical Engineer'sHandbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59 ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7,line 19, and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col.7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140,162-164, 166, 167, and 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Col. 3, line 66 throughCol. 5, line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc.,New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

Unless otherwise indicated, all parts are by weight in the followingexamples.

EXAMPLE 9

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             65%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide                                                            dodecylphenol polyethylene glycol ether                                                                2%                                                   sodium ligninsulfonate   4%                                                   sodium silicoaluminate   6%                                                   montmorillonite (calcined)                                                                             23%                                                  ______________________________________                                    

The ingredients are thoroughly blended. The liquid surfactant is addedby spraying upon the solid ingredients in the blender. After grinding ina hammer mill to produce particles essentially all below 100 microns,the material is reblended, sifted through a U.S.S. No. 50 sieve (0.3 mmopening) and packaged.

EXAMPLE 10

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             50%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-5-(trifluoromethoxy)-                                          benzenesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                       2%                                                   low-viscosity methyl cellulose                                                                         2%                                                   diatomaceous earth       46%                                                  ______________________________________                                    

The ingredients are blended, coarsely hammer milled and then air milledto produce particles of active ingredient all below 10 microns indiameter. The product is reblended before packaging.

EXAMPLE 11

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable powder of Example 10                                                                       10%                                                     attapulgite granules  90%                                                     ______________________________________                                    

A slurry of wettable powder containing 50% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 12

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             80%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-5-(trifluoromethoxy)-                                          benzenesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                       2%                                                   sodium ligninsulfonate   2%                                                   synthetic amorphous silicate                                                                           3%                                                   kaolinite                13%                                                  ______________________________________                                    

The ingredients are blended and coarsely ground in a hammer mill toproduce particles essentially all below 100 microns in size. Thematerial is reblended, sifted through a U.S.S. No. 50 sieve (0.3 mmopening) and packaged.

EXAMPLE 13

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             25%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-5-(trifluoromethoxy)-                                          benzenesulfonamide                                                            anhydrous sodium sulfate 10%                                                  crude calcium ligninsulfonate                                                                           5%                                                  sodium alkylnaphthalenesulfonate                                                                        1%                                                  calcium/magnesium bentonite                                                                            59%                                                  ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to passthrough a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on aU.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and thefines recycled.

EXAMPLE 14

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             25%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-5-(trifluoromethoxy)-                                          benzenesulfonamide                                                            polyethylene sorbitol hexaoleate                                                                        5%                                                  highly aliphatic hydrocarbon oil                                                                       70%                                                  ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingsuspension may be applied directly, but preferably after being extendedwith oils or emulsified in water.

EXAMPLE 15

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        5-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                                             40%                                                  aminocarbonyl]-2-(trifluoromethoxy)-                                          benzenesulfonamide; and                                                       2-Chloro-N--[(4,6-dimethylpyrimidin-2-yl)-                                    aminocarbonyl]-5-(trifluoromethoxy)-                                          benzenesulfonamide                                                            sodium ligninsulfonate   1.5%                                                 low-viscosity methyl cellulose                                                                          3%                                                  attapulgite              54%                                                  ______________________________________                                    

The ingredients are thoroughly blended, passed through an air mill, toproduce an average particle size under 15 microns, reblended, and siftedthrough a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

UTILITY

The compounds of Formula I are useful as herbicides. They may be appliedeither pre- or postemergence for the control of undesired vegetation innoncrop areas or for selective weed control in certain crops, e.g.wheat. Some of these compounds are useful for the pre- and/orpostemergence control of nutsedge. By properly selecting rate and timeof application, compounds of this invention may be used to modify plantgrowth beneficially.

The precise amount of the compound of Formula (I) to be used in anygiven situation will vary according to the particular end resultdesired, the use involved, the weeds to be controlled, the soil type,the formulation and mode of application, weather conditions, etc. Sinceso many variables play a role, it is not possible to state a rate ofapplication suitable for all situations. Broadly speaking, the compoundsof this invention are used at levels of about 0.01 to 20 kg/ha with apreferred range of 0.1 to 10 kg/ha. The lower rates of the range willgenerally be selected for lighter soils, for selective weed control incrops, or in situations where maximum persistence is not necessary. Someof the compounds of Formula (I) can be used at very low rates for plantgrowth modification, but higher rates may also be useful, depending onfactors such as the crop being treated, timing of treatment, etc.

The compounds of Formula (I) may be combined with other herbicides andare particularly useful in combination with3-(3,4-dichlorophenyl)-1,1-dimethylurea, the triazines such as2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, the uracils suchas 5-bromo-3-sec-butyl-6-methyluracil, N-(phosphonomethyl)glycine,3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione,N,N-dimethyl-2,2-diphenylacetamide, 2,4-dichlorophenoxyacetic acid (andclosely related compounds), 4-chloro-2-butynyl-3-chlorophenylcarbamate(Carbyne®), diisopropylthiolcarbamic acid, ester with 2,3-dichloroallylalcohol (Avadex®), diisopropylthiolcarbamic acid,S-(2,3,3-trichloroallyl) ester (Avadex® BW),ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (Suffix®),1,2-dimethyl-3,5-diphenylpyrazolium methyl-sulfate (Avenge®), methyl2-[4-(2,4-dichlorophenoxy)-phenoxy]-propanoate (Hoelon®),4-amino-6-tertbutyl-3-(methylthio)-1,2,4-triazin-5(4H)-one (Lexone®),3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Lorox®),3-isopropyl-1H-2,1,3-benzothiodiazin-(4)-3H-one 2,2-dioxide,α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine,1,1'-dimethyl-4,4'-bipyridinium ion, monosodium methanearsonate,2-chloro-2',6'-diethyl-(methoxymethyl)acetanilide, and1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea (Cotoran®).

The activity of these compounds was discovered in greenhouse tests. Thetests are described below and the data resulting from them are shownbelow.

TEST PROCEDURE

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), Cassia tora, morningglory (Ipomoeasp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice, wheat andnutsedge tubers were planted in a growth medium and treated preemergencewith the chemicals dissolved in a nonphytotoxic solvent. At the sametime, cotton having five leaves (including cotyledonary ones), bushbeans with the third trifloiate leaf expanding, crabgrass with twoleaves, barnyardgrass with two leaves, wild oats with one leaf, cassiawith three leaves (including cotyledonary ones), morningglory with fourleaves (including cotyledonary ones), cocklebur with four leaves(including cotyledonary ones), sorghum with three leaves, corn withthree leaves, soybean with two cotyledonary leaves, rice with twoleaves, wheat with one leaf, and nutsedge with three-five leaves weresprayed. Treated plants and controls were maintained in a greenhouse for16 days, then all species were compared to controls and visually ratedfor repsonse to treatment.

Ratings for compounds tested by this procedure are recorded in Table A.

0=no effect

10=maximum effect

C=chlorosis or necrosis

E=emergence inhibition

G=growth retardation

H=formative effects

U=unusual pigmentation

    TABLE A      POSTEMERGENCE     MORN-     BARN-        Rate BUSH- COT- ING- COCK-     CAS- NUT- CRAB- YARD- WILD   SOY-    kg/ha BEAN TON GLORY LEBUR SIA     SEDGE GRASS GRASS OATS WHEAT CORN BEAN RICE SORGHUM      ##STR75##      2/5 9C 9C 10C 9C 8C 9C 2C 5G 3C 9H 1C 5G 1C 2C 8H 4C 9G 3C 8G 2C 9G      ##STR76##      0.4 9C 9C 9C 9C 9C 9G 9C 5C,9H 2C,9G 1C,9G 5U,9G 5C,9G 5C,9G 3U,9G      ##STR77##      0.4 9D,9G,6Y 5C,9G 10C 9C 9C 5G 0 2G 0 0 3G 5C,9G -- 3G      ##STR78##      0.4 9D,9G,6Y 5C,9G 6C,9G 9C 5C,9G 9C 1C 1C,2H 0 0 1C 2C,9G -- 1C,7G      ##STR79##      0.4 9C 6C,9G 10C 10C 3C,8G 1C,9G 1C 1C,4G 1C 1C 7H 2C,9G -- 2C,9H      ##STR80##      0.4 3C,8G,6Y 3C,9G 9C 3C,9G 0 0 0 0 0 0 0 2C,2H, 5G 0 0      ##STR81##      0.4 3C,8G,6Y 3C,4H,9G 10C 10C 1C 1C,6G 4G 2G 2G 3G 1C,3G 1C,8G 1C,5G     1C,4G      ##STR82##      0.4 3C,7G,6Y 4C,9G 9C 9C 2C 1C 2G 1C 0 0 3G 2C,8G 3G 2G      ##STR83##      0.4 2C,4G 2C,2H 2C,8G 2C,8G 1C 0 0 0 0 0 0 1H 0 0      ##STR84##      0.4 6C,9G 5C,9G 3C,9G 9C 2C,6H 8G 1C,5G 1C,5H 5G 3G 0 9C 6G 1H,6G      ##STR85##      0.4 4C,9G,6Y 3C,4H 2C,5G 3C,5G 1C,3G 4G 2G 1C,5G 0 0 2G 1C,3G 3G 1C,3G      ##STR86##       0.4 10G,5C 8G,3H,5C 10C 10C 3G 0 0 0 0 0 0 10G,7C 0 0      ##STR87##      0.4 4G,2C 0 10G,7C 7G,5H 0 0 0 0 0 0 0 0 0 0      ##STR88##      0.4 10G,3H,4C 6G,3H,3C 10C 3C 2C 0 0 0 0 0 0 10G,6C 0 0      ##STR89##      0.4 10G,7C 7G,3H,3C 10C 10G,7C 3C 3G 0 0 0 0 0 10G,5C 0 0       PRE-EMERGENCE   MORNING- COCK-  NUT- CRAB- BARNYARD- WILD   SOY-     Rate kg/ha GLORY LEBUR CASSIA SEDGE GRASS GRASS OATS WHEAT CORN BEAN     RICE SORGHUM      ##STR90##      2/5 9G 9G 2C 9G 10E 4G 3C 9H 2C 8G 8G 1U 9G 9H 9H 2C 9H      ##STR91##      0.4 9G 9H 9G 10E 3C,9G 9H 2C,9H 9H 9G 9H 10E 5C,9H      ##STR92##      0.4 9G 9G 5C,9G 0 0 2C 0 0 1C,6G 9H 1C,7G 6G      ##STR93##      0.4 9G 9G 9G 10E 2G 2C,8H 0 0 1C,7G 9H 8G 9H      ##STR94##      0.4 8G 9G 9G 10E 0 2C,8H 9G 2G 9H 9H 9H 9H      ##STR95##      0.4 1C,7G 8H 1C 0 0 4C 0 0 1C,5G 2H 0 0      ##STR96##      0.4 1C,7G 9G 8G 3G 0 0 0 0 1C,6G 1C,4G 2G 1C,3G      ##STR97##      0.4 9G 9G 2G 3G 0 0 0 0 1C,6G 1C 1C,2G 1C,5G      ##STR98##      0.4 7G 7G 0 0 0 1C 0 0 1C 2G 2C 0      ##STR99##      0.4 8G 10E 8G 10E 1C,7G9H1C,7H 1C,6G 9G 9H 10E 3C,9H      ##STR100##      0.4 7G 10E 8G 10E 3G 1C,4G 2G 2G 1C,5G 1H 9H 1C,6G      ##STR101##      0.4 8G,9C 7G,7C 0 0 0 0 0 0 0 7G,5H 0 0      ##STR102##      0.4 0 8G,9C 0 0 0 0 0 0 0 0 0 4G,2H      ##STR103##      0.4 4G 5G,5H 5G 3G 4G 3G 0 0 0 1C 3C 4G      ##STR104##      0.4 8G6G,5H 7G8G0 3G 0 0 3G4G,3H 3C4G,3H

TEST B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus),morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sidaspinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Daturastramonium). A 12.5 cm diameter plastic pot was also filled withprepared soil and planted with rice and wheat. Another 12.5 cm pot wasplanted with sugarbeets. The above four containers were treatedpreemergence with test compounds within the scope of this invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described for test A. The data are summarized in Table B.Note that certain compounds are useful as preemergence treatments forweed control in wheat.

    TABLE B      PRE-EMERGENCE ON FALLSINGTON SILT LOAM        Rate  Barnyard-   Johnson- Dallis-  Ky.    Cockle-  kg/ha Crabgrass     grass Sorghum Wild Oats grass grass Giant Foxtail Bluegrass Cheatgrass     Corn Mustard bur      ##STR105##        mixture with 1/16 4G 6G 7G 3H 4G 6G 7G 5G 7G 5C 7G 8G 5H 8G 9C 8G 5C     1/4 4G 8G 4C 10C 6G 3C 8G 5C 7G 10C 9G 9C 9C 8G 5H 9G 9C 9G 8C      ##STR106##      ##STR107##      0.060.25 00 02C 6G,3H9G,9C 4G6G 6G,3H8G,3H 3G5G 3G6G 5G7G,4C 5G7G     3G8G,3H 10C10C --7G      ##STR108##      0.030.12 5G7G,3H 8G,5H8G,5H 10C10E 6G6G 7G,5H8G,8H 9G,5H9G,5H 4G7G,10H     7G7G,3C 5G,4C7G,3H 5G,3H8G,7H 9G,9C10C 5G5G,2H      ##STR109##      0.060.25 00 00 05G,3H 03G 05G,3H 00 03G 04G,2C 2G5G,3C 00 8G,3C8G,8C     03H   Rate kg/ha Pigweed Nutsedge Morningglory Cassia Teaweed Velvetleaf J     imsonweed Soybean Rice Wheat Sugarbeets Cotton      ##STR110##         mixture with 1/16 -- 10E 8G 7G 10C 9G 8C 4G 7G 5H 6G 0 7G 7G 5H  1/4     -- 10E 8G 7G 10C 10C 5G 3C 8G 5H 8G 5C 2G 8G 5C 8G      ##STR111##      ##STR112##      0.060.25 ---- 8G10E 4G8G 5G7G,5C ---- 10C10C 00 6G,5H6G,5H 6G,7C5G,5C     5G,2C4G,2C 7G10C 3G6G,2H      ##STR113##      0.030.12 ---- 7G8G 5G7G 8G,6C8G,6C 4G6G,5C 7G,5C10C 5G,3C6G,5C 7G,5H7G,5     H 7G,5H10C 5G5G,2C 7G,3H7G,5H 7G,5H8G      ##STR114##      0.060.25 ---- 7G10E 00 00 06G 02G 03G 00 5G 6G 03G 4G5G 02G

TEST C

Purple nutsedge (Cyperus rotundus) tubers were planted about 2 cm deepin Fallsington silt loam soil contained in 10 cm diameter plastic pots.Five tubers were planted in each pot. Compounds of this invention weredissolved in a non-phytotoxic diluent and sprayed at 560 l/ha in fourmethods of application: soil surface, tuber/soil, soil incorporated, andpostemergence. The soil surface spray consisted of spraying the compoundon the surface of the firmed covering soil. The tuber/soil sprayconsisted of spraying the compound on exposed tubers and subtending soilbefore adding the untreated covering soil. Soil incorporated treatmentconsisted of mixing the compound with the covering soil before using itto cover the tubers. The postemergence treatment was sprayed on nutsedgefoliage and the surrounding soil surface when nutsedge had emerged andgrown to a height of about 12 cm. Pots receiving the postemergencetreatment were placed directly in the greenhouse. Pots receiving theother treatments were misted with about 0.3 cm water before beingtransferred to the greenhouse. Response ratings assessed after fourweeks are recorded in Table C based on the same rating system asdescribed in procedure A.

                  TABLE C                                                         ______________________________________                                         ##STR115##                                                                    ##STR116##                                                                   Response Rating (after 4 weeks)                                               Rate   Preemergence                                                                              Tuber    Soil Incor-                                                                           Post-                                     kg/ha  Soil Surface                                                                              Spray    poration                                                                              emergence                                 ______________________________________                                        .008   5G          5G       6G      5G                                        .031   8G          8G       9G      5C 9G                                     .125   10E         8E 9G    10E     6C 9G                                     ______________________________________                                    

TEST D

Twenty-five cm diameter plastic pots filled with Fallsington silt loamwere planted with soybeans, cotton, alfalfa, corn, rice, wheat, sorghum,velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), Cassia(Cassia tora), morningglory (Ipomoea hederacea), jimsonweed (Daturastramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitariaspp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloacrusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua).Approximately two weeks after planting, the young plants and the soilaround them were sprayed overall with the test chemicals dissolved in anonphytotoxic solvent. Two weeks after treatment, all species werecompared to untreated controls and visually rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table D. Several of the compounds tested by thisprocedure are useful for the post-emergence control of weeds in wheat,corn and rice.

    TABLE D        Vel- Ses-   Morn- Al- Jim- Cock-     Barn-  Giant   Rate Soy- vet-     ban- Cas- Cot- ing- fal- son- le-  Crab-  Nut- yard-  Fox- Wild Sor-     kg/ha beans leaf ia sia ton glory fa weed bur Corn grass Rice sedge     grass Wheat tail Oats ghum      ##STR117##       mixture with 0.25 10G, 10C 10G, 9G, 8G, 10G, 8G, 3G 10C 7G, 0 6G,     10G,5C 4G,2C 0 0 6G 9G,5H   8C  8C 4C 4C 7C 5C   3H  2C  0.06 10G, 10C     8G, 7G, 8G, 7G 8G, 0 10G, 5G, 0 6G 10G,3C 0 0 0 3G 8G,5H8G4C3C 4C  4C     8C 3H      ##STR118##      ##STR119##      0.250.06 10G,6C10G,6C 9C9C 10G,8C10G,8C 10G,8C10G,7C 10G,7C10G,7C     10C10C 8C7C ---- 10C10C 1G,1H1G,2H 2G0 2G, 1C0 5G6G 3G,1C3G,1C 00 00 1G0 1     G0      ##STR120##      0.250.06 10G,7C10G,5C 9G,6C6G,2C 9C10G,8C 10G,7C10G,6C 10G,6C10G,6C     8     10G,C10G,9C 7C4C ---- 10G,8C10G,7C 1G,1H0 1G1G 1G0 9G,1C8G,2C 3G,1C4G,1C 0    0      ---- 1G0 4G,2C5G,3C      ##STR121##      0.250.063 10G,7C10G,6C 10G,9C10G,8C 10G,7C10G,7C 10G,8C10G,7C 10G,6C8G,3     C 10G,8C10G,6C 5G,3C5G,3C 4G,3C0 10G,7C9G,4C 5G,3C2G,1C 3G,1C0 8G,2C6G,1C      8G,1C5G 2G,1C2G,1C 5G2G 5G,2C4G 7G,1C4G 6G,2C4G,1C      ##STR122##      0.250.060.070.015 9G,3C8G,2C10G,6C9G,4C 10C3G,3C3G,1C3G 9C9G,3C8G,5C8G,3     C 9G,3C5G,2C3G,1C1G,1C 9G,5C6G,3C6G,3C6G,2C 9G,7C8G,6C7G,2H7G 6C5C6G,2C2G     ,2C ------4G 10G,8C9G,9C7G,2C6G,1C 2G2G00 2G02G,1C0 9G,3C6G,1C3G2G       7     9G9G6GG 4G,1C3G,1C2G1G 1G1G00 003G2G 4G3G00 9G,3C9G,3C 5G,2C4G      ##STR123##      0.1250.0310.008 10G,7C10G,7C10G,7C 10G,8C10G,7C10G,5C 10C9C10G,6C       1     10G,8C0G,8C10G,8C 10G,9C10G,8C9G,6C 10G,7C8G,4C6G 7C6C6G,2C 9G,4C6G,3C6G,2     C 10G,9C9G,5C9G,3C 9G,3C9G,4H7G,5H 8G7G2G 8G,3C8G,2C8G,2C 10G9G,2C8G,4C     10G,6C10G,6C8G,2C 9G,3C 7G,2C2G ----6G,1C 7G7G,2C7G,2C 9G,4C9G,2C10G,4C      ##STR124##      0.50.125 10G,5C10G,5C 10G,7C9G,4C 10G,7C10G,6C 5G,2C5G,2C 7G,3C7G,3C     10G,8C10G,7C 7G,2C10G,8C 9G,6C9G,5C 10G,8C10G,8C 00 00 4G2G 6G6G 1G1G     --0 00 00 1G1G      ##STR125##      0.50.125 10G,6C10G,6C 10G,7C10G,6C 9G,5C9G,4C 7G,3C6G,3C 8G,4C7G,3C     8     10G,C10G,8C 7G,3C9G,4C 7G,2C7G 10G,7C9G,6C 1G0 1G0 3G,1C3G,1C 8G,2C7G,1C 1     G0 00 00 00 1G1G      ##STR126##      0.50.125 10G,5C7G,3C 10G,7C4G,1C 9G,7C9G,3C 6G,3C5G,1C 8G,4C5G,2C     10C10G,8C 4G,3C2G,2C 7G,3C1C 9G,5C9G,3C 1G0 2G2G,1C 5G,1C7G,2C 8G,1C7G,1C      2G0 00 3G,1C1C 1G0 1G1G

TEST E

Fifteen and twenty-five cm diameter plastic pots filled with Fallsingtonsilt loam were planted with corn (Zea mays), cocklebur (Xanthiumpennsylvanicum), morningglory (Ipomea hederacea), field bindweed(Convolulus arvensis), smartweed (Polygonum spp.), jimsonweed (Daturastramonium), lambsquaters (Chenopodium album), cassia (Cassia tora),pigweed (Amaranthus retroflexus), johnsongrass (Sorghum halepense),barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii),crabgrass (Digitaria spp.) and nutsedge (Cyperus rotundus). Varying fromtwo to three weeks after planting, the young plants and the soil aroundthem were sprayed overall with the test chemicals dissolved in anonphytotoxic solvent. Two weeks after treatment, all species werecompared to untreated controls and visually rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table E. The compounds tested by this procedureshow possible usefulness for postemergence control of weeds in corn.

                                      TABLE E                                     __________________________________________________________________________             ##STR127##                                                                                             ##STR128##                                  Rate kg/ha                                                                            1/32        1/3          1/32        1/8                              __________________________________________________________________________    Corn    0           2G,1C        1G          2G                               Cocklebur                                                                             10G,8C      10G,9C       10C         10C                              Morningglory                                                                          10C         10C          10G,9C      10G,9C                           Field Bindweed                                                                        8C          10C          8C          10C                              Smartweed                                                                             10G,7C      10G,8C       10G,7C      10G,9C                           Jimsonweed                                                                            9G,6C       9G,6C        6G          8G,3C                            Lambsquarter                                                                          9G,5C       10G,6C       7G          8G,3C                            Cassia  19G,7C      10G,7C       10G,7C      10G,7C                           Pigweed 9G,3C       10G,7C       9G,3C       10G,8C                           Johnnsongrass                                                                         3G          --           2G,1U       7G,3U                            Barnyardgrass                                                                         0           1G           1G          2G,1C                            Giant Foxtail                                                                         0           0            3G          4G                               Crabgrass                                                                             0           0            1G          2G                               Nutsedge                                                                              0           0            7G,2C       8G,3C                            __________________________________________________________________________

TEST F

The following table, Table F, is presented to additionally illustratethe biological activity of the compounds of the present invention. Thedata illustrate the efficacy of the compounds for the control of weedsin rice cultures.

Rice plants 10.5 cm tall were transplanted into paddies containing soil,sprouting barnyardgrass (Echinochloa crusgalli), seeds, sprouting waterchestnut (Eleocharis spp.) tubers, arrowhead (Sagittaria latifolia)tubers, and Scirpus mucronatus seeds. The test compound was applieddirectly into the water, which was maintained at a few centimeters abovethe soil surface. Ratings (same system as in Table A) were taken on ricefour days after application; ratings were taken for all speciesincluding rice four weeks after application.

                  TABLE F                                                         ______________________________________                                         ##STR129##                                                                   Rate Rice   Rice   Barnyard-                                                                             Water  Arrow- Scirpus                              kg/  4      4      grass   Chestnut                                                                             head   mucronatus                           ha   days   wks    4 weeks 4 weeks                                                                              4 weeks                                                                              4 weeks                              ______________________________________                                         25  0      0      2G      10G    10E    10C                                  100  0      0      7G      10G,5C 10E    10C                                  ______________________________________                                    

What is claimed is:
 1. A compound selected from ##STR130## wherein W isO or S;R is CHF₂, CF₃, CH₂ CF₃ or CF₂ CHFG, where G is F, Cl, CF₃ or Br;A is O or S(O)_(n), where n is 0, 1 or 2; R¹ is H, F, Cl, Br or CH₃ ; Xis CH₃ or OCH₃ ; Y is CH₃, OCH₃, OCH₂ CH₃, (CH₂)_(m) OCH₃ (where m is 1or 2), OCH₂ CH₂ OCH₃, or OCHR² CO₂ R³, where R² is H or CH₃ and R³ isCH₃ or C₂ H₅ ; and E is CH and agriculturally suitable salts thereof. 2.A compound of claim 1 wherein W is O.
 3. A compound of claim 2 wherein Yis CH₃ or CH₃ O.
 4. A compound of claim 3 wherein A is O, S or SO₂.
 5. Acompound of claim 3 wherein R¹ is H or Cl.
 6. A compound of claim 3wherein R¹ is H or Cl.
 7. The compound of claim 1,5-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(trifluoromethoxy)benzenesulfonamide.8. The compound of claim 1,2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-5-(trifluoromethoxy)benzenesulfonamide.9. The compound of claim 1,N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide.10. The compound of claim 1,N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide.11. The compound of claim 1,N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(1,1,2,2-tetrafluoroethoxy)benzenesulfonamide.12. A mixture of a compound of claim 1 consisting essentially of5-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(trifluoromethoxy)benzenesulfonamide,and2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]-5-(trifluoromethoxy)benzenesulfonamide.13. A composition for the control of undesirable vegetation consistingessentially of a compound of claim 1 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 14. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 2 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 15. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 3 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 16. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 4 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 17. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 5 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 18. Acomposition for the control of undesirable vegetation consistingessentially of the compounds of claim 12 and at least one of (a) asurface-active agent and (b) a solid or liquid diluent.
 19. A method forcontrol of undesirable vegetation comprising applying to the locus ofsuch undesirable vegetation a herbicidally effective amount of acompound of claim
 1. 20. A method for control of undesirable vegetationcomprising applying to the locus of such undesirable vegetation aherbicidally effective amount of a compound of claim
 2. 21. A method forthe control of undesirable vegetation comprising applying to the locusof such undesirable vegetation a herbicidally effective amount of acompound of claim
 3. 22. A method for the control of undesirablevegetation comprising applying to the locus of such undesirablevegetation a herbicidally effective amount of a compound of claim
 4. 23.A method for the control of undesirable vegetation comprising applyingto the locus of such undesirable vegetation a herbicidally effectiveamount of a compound of claim
 5. 24. A method for the control ofundesirable vegetation comprising applying to the locus of suchundesirable vegetation herbicidally effective amount of the compounds ofclaim 6.